Method for precise molding and alignment of structures on a substrate using a stretchable mold

ABSTRACT

A method for molding and aligning microstructures on a patterned substrate using a microstructured mold. A slurry containing a mixture of a ceramic powder and a curable fugitive binder is placed between the microstructure of a stretchable mold and a patterned substrate. The mold can be stretched to align the microstructure of the mold with a predetermined portion of the patterned substrate. The slurry is hardened between the mold and the substrate. The mold is then removed to leave microstructures adhered to the substrate and aligned with the pattern of the substrate. The microstructures can be thermally heated to remove the binder and optimally fired to sinter the ceramic powder.

TECHNICAL FIELD

The present invention generally relates to methods of forming andaligning structures on patterned substrates. More specifically, thepresent invention relates to methods of molding and aligning glass,ceramic, and/or metal structures on patterned substrates for displayapplications, and to displays having barrier ribs molded and alignedusing a stretchable mold.

BACKGROUND

Advancements in display technology, including the development of plasmadisplay panels (PDPs) and plasma addressed liquid crystal (PALC)displays, have led to an interest in forming electrically-insulatingceramic barrier ribs on glass substrates. The ceramic barrier ribsseparate cells in which an inert gas can be excited by an electric fieldapplied between opposing electrodes. The gas discharge emits ultraviolet(uv) radiation within the cell. In the case of PDPs, the interior of thecell is coated with a phosphor which gives off red, green, or bluevisible light when excited by uv radiation. The size of the cellsdetermines the size of the picture elements (pixels) in the display.PDPs and PALC displays can be used, for example, as display screens inhigh definition television (HDTV) or other digital electronic displays.

Various methods have been used to fabricate ceramic barrier ribs forPDPs. One method is repeated screen printing. In this method, a screenis aligned on the substrate and used to print a thin layer of barrierrib material. The screen is removed and the material is hardened.Because the amount of material that can be printed with this techniqueis insufficient to create ribs having the desired height (typicallyabout 100 μm to 200 μm), the screen is then realigned and a second layerof barrier rib material is printed on top of the first layer. The secondlayer is then hardened. Layers of rib material are repeatedly printedand hardened until the desired barrier height is achieved. The multiplealignment and hardening steps required with this method results in along processing time and poor control of the overall barrier rib profileshape.

Another method involves masking and sandblasting. In this method, asubstrate having electrodes is coated with the barrier rib materialwhich is partially fired. A mask is then applied to the barrier materialusing conventional lithography techniques. The mask is applied on theareas between the electrodes. The substrate is then sandblasted toremove the barrier rib material exposed by the mask. Finally, the maskis removed and the barrier ribs are fired to completion. This methodrequires only one alignment step and can therefore be more accurate thanthe multiple screen printing method. However, because the area of thefinished substrate covered by barrier ribs is small, most of the barrierrib material must be removed by sandblasting. This large amount of wasteincreases the production cost. In addition, because the barrier ribmaterial often includes lead-based glass frit, environmentally-friendlydisposal of the removed material is an issue. Also, while the positionsof the ribs after sandblasting can be quite accurate, the overall shapesof the ribs, including the height-to-width aspect ratio, can bedifficult to control.

Another process utilizes conventional photolithographic techniques topattern the barrier rib material. In this technique, the barrier ribmaterial includes a photosensitive resist. The barrier rib material iscoated onto the substrate over the electrodes, often by laminating therib material in the form of a tape onto the substrate. A mask is appliedover the barrier rib material and the material is exposed by radiation.The mask is removed and the exposed areas of the material are developed.Barrier rib material can then be removed by washing to form the ribstructures. This process can give high precision and accuracy. However,as with sandblasting, much material is wasted because the entiresubstrate is initially coated with the barrier rib material and the ribsare patterned by material removal.

Another process involves using a mold to fabricate barrier ribs. Thiscan be done by direct molding on the substrate or by molding on atransfer sheet and then transferring the ribs to a substrate. Directmolding onto a substrate involves coating either the substrate or themold with barrier rib material, pressing the mold against the substrate,hardening the material on the substrate, and removing the mold. Forexample, Japanese Laid-Open Patent Application No. 9-134676 disclosesusing a metal or glass mold to shape barrier ribs from a glass orceramic powder dispersed in a binder onto a glass substrate. JapaneseLaid-Open Patent Application No. 9-147754 disclosed the same processwhere electrodes are transferred to the substrate simultaneously withthe barrier ribs using a mold. After hardening the barrier rib materialand removing the mold, the barrier ribs are fired to remove the binder.

European Patent Application EP 0 836 892 A2 describes printing a mixtureof a glass or ceramic powder in a binder onto a transfer sheet. Thematerial is printed using a roll or plate intaglio to form barrier ribshapes on the transfer sheet. A substrate is then pressed against therib material on the transfer sheet to adhere the material to thesubstrate. After curing the rib material on the substrate, the ribs arefired. The transfer film can be removed before firing or burned awayduring firing.

SUMMARY OF THE INVENTION

While direct molding offers less wasted material than sandblasting orlithography and fewer alignment steps than screen printing, it poseschallenges such as releasing the mold consistently and repeatedly fromthe barrier rib material and fabricating a separate mold for each uniquedisplay substrate. For example, slight adjustments in barrier rib pitchdimensions are desired to account for variations in shrinkage factors ofglass substrates due to, for example, different lots or differentsuppliers.

If the barrier ribs are initially molded onto a transfer sheet, thismethod has the same disadvantages as direct molding. In addition, thetransfer sheet with the rib material must be aligned with the electrodeson the substrate. This printing method may be used to print a pattern ona flexible film where the pattern on the film can subsequently be usedas a mold for direct molding of barrier ribs. One difficulty, however,is that when the mold and rib material are pressed against the substrateto adhere the rib material to the substrate, the mold tends to elongate.This motion of the mold make precise alignment across the substrate verydifficult. The method disclosed for solving this problem is to deposit ametal layer on the back of the mold to keep the mold from being able toelongate.

The present invention provides a method for forming and aligningmicrostructures on patterned substrates. Preferred embodiments of thepresent invention permit formation and alignment of microstructures onpatterned substrates with high precision and accuracy over relativelylarge distances.

In a first aspect, the method of the present invention is a process forforming and aligning microstructures on a patterned substrate whichproceeds by first placing a mixture comprising a curable materialbetween a patterned substrate and a patterned surface of a mold. Thepatterned surface of the mold has a plurality of microstructuresthereon. Microstructure as used in this application refers toindentations or protrusions in the surface of the mold. The mold isstretched to align a predetermined portion of the patterned surface ofthe mold with a correspondingly predetermined portion of the patternedsubstrate. The curable material between the mold and the substrate iscured to a rigid state adhered to the substrate. The mold is thenremoved, leaving hardened structures of the mixture aligned with thepattern of the substrate, the hardened structures replicating themicrostructures of the patterned surface of the mold.

In another aspect, the present invention is a process for forming andaligning ceramic microstructures on a patterned substrate. A slurry isprovided, the slurry being a mixture of a ceramic powder and a curablefugitive binder. The slurry is placed between a patterned glasssubstrate and a patterned surface of a mold, the patterned surface ofthe mold having a plurality of microstructures thereon. The mold isstretched to align a predetermined portion of the patterned surface ofthe mold with a correspondingly predetermined portion of the patternedsubstrate. The curable binder of the slurry is cured to harden theslurry and to adhere the slurry to the substrate. Then the mold isremoved to leave green state microstructures of the slurry adhered tothe substrate, the green state microstructures substantially replicatingthe microstructures of the patterned surface of the mold. The greenstate microstructures may be thermally processed to form substantiallydense ceramic microstructures.

In another aspect, the present invention is a substrate element for usein an electronic display having microstructured barrier ribs molded andaligned on a patterned portion of a substrate. For example, the presentinvention provides a high definition television screen assemblyincluding a plasma display panel. The plasma display panel includes aback glass substrate having a plurality of independently addressableelectrodes forming a pattern and a plurality of ceramic microstructuredbarriers molded and aligned with the electrode pattern on the backsubstrate according to the process of the present invention. Phosphorpowder is deposited between the ceramic barriers, and a front glasssubstrate having a plurality of electrodes is mounted with itselectrodes orthogonally facing the electrodes of the back substrate. Aninert gas is disposed between the front and back substrates.

In yet another aspect, the present invention provides an apparatus formolding and aligning ceramic microstructures on a patterned substrate.The apparatus stretches a stretchable mold having a microstructurethereon into close proximity with a patterned substrate, registers andaligns the microstructure of the mold with a predetermined portion ofthe patterned substrate, applies a slurry comprising a ceramic powderdispersed in a curable binder between the microstructure of the mold andthe substrate, stretches the mold to align the microstructure of themold with the predetermined portion of the patterned substrate, andcures the binder of the slurry between the substrate and the mold.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a plasma display panel assembly.

FIG. 2 is a cross-sectional schematic of a slurry disposed between amold and a patterned substrate.

FIG. 3 is a schematic representation of a method of stretching astructured mold according to the present invention.

FIG. 4 is a schematic representation of a method of removing a mold fromgreen state microstructures.

FIG. 5 is a schematic representation of ceramic microstructures moldedand aligned on a patterned substrate.

FIG. 6 is a schematic representation of an apparatus for molding andaligning microstructures.

FIG. 7 is a schematic of a jig used to stretch a mold.

DETAILED DESCRIPTION

The method of the present invention enables accurate molding ofmicrostructures on a patterned substrate. While the method of thepresent invention can be used to mold and align microstructures made ofvarious curable materials onto various patterned substrates for variousapplications, it is convenient to describe aspects of the method interms of a particular application, namely molding and aligning ceramicbarrier rib microstructures on an electrode-patterned substrate. Ceramicbarrier rib microstructures are particularly useful in electronicdisplays in which pixels are addressed or illuminated via plasmageneration between opposing substrates, such as PDPs and PALC displays.References to ceramic microstructure applications in the description ofthe method of the present invention that follows serve to illustrateaspects of the present invention and should not be read to limit thescope of the present invention or of the claims recited.

As used herein, the term ceramic refers generally to ceramic materialsor glass materials. Thus, in the slurry used in one aspect of the methodof the present invention, the included ceramic powder can be glass orceramic particles, or mixtures thereof. Also, the terms fusedmicrostructures, fired microstructures, and ceramic microstructuresrefer to microstructures formed using the method of the presentinvention which have been fired at an elevated temperature to fuse orsinter the ceramic particles included therein.

In an illustrative aspect, the method of the present invention includesusing a slurry which contains a ceramic powder, a curable organicbinder, and a diluent. The slurry is described in copending and cofiledU.S. patent application Ser. No. 09/221,007, filed Dec. 23, 1998, whichis incorporated herein by reference. When the binder is in its initialuncured state, the slurry can be shaped and aligned on a substrate usinga mold. After curing the binder, the slurry is in at least a semi-rigidstate which can retain the shape in which it was molded. This cured,rigid state is referred to as the green state, just as shaped ceramicmaterials are called “green” before they are sintered. When the slurryis cured, the mold can be removed from the green state microstructures.The green state material can subsequently be debinded and/or fired.Debinding, or burn out, occurs when the green state material is heatedto a temperature at which the binder can diffuse to a surface of thematerial and volatilize. Debinding is usually followed by increasing thetemperature to a predetermined firing temperature to sinter or fuse theparticles of the ceramic powder. After firing, the material can bereferred to as fired material. Fired microstructures are referred toherein as ceramic microstructures.

FIG. 1 shows the substrate elements of a plasma display panel. The backsubstrate element, oriented away from the viewer, has a glass substrate10 with independently addressable parallel electrodes 12. Ceramicbarrier ribs 14 are positioned between electrodes and separate areas inwhich red (R), green (G), and blue (B) phosphors are deposited. Thefront substrate element includes a glass substrate 100 and a set ofindependently addressable parallel electrodes 102. The front electrodes102, also called sustain electrodes, are oriented perpendicular to theback electrodes 12, also referred to as address electrodes. In acompleted display, the area between the front and back substrateelements is filled with an inert gas. To light up a pixel, an electricfield is applied between crossed sustain and address electrodes withenough strength to excite the inert gas atoms therebetween. The excitedinert gas atoms emit uv radiation which causes the phosphor to emit red,green, or blue visible light.

Back substrate 10 is preferably a transparent glass substrate.Typically, substrate 10 is made of soda lime glass which can optionallybe substantially free of alkali metals. The temperatures reached duringprocessing can cause migration of the electrode material in the presenceof alkali metal in the substrate. This migration can result inconductive pathways between electrodes, thereby shorting out adjacentelectrodes or causing undesirable electrical interference betweenelectrodes known as “crosstalk.” The substrate should be able towithstand the temperatures required for sintering, or firing, theceramic barrier rib material. Firing temperatures may vary widely fromabout 400° C. to 1600° C., but typical firing temperatures for PDPmanufacture onto soda lime glass substrates range from about 400° C. toabout 600° C., depending on the softening temperature of the ceramicpowder in the slurry. Front substrate 100 is a transparent glasssubstrate which preferably has the same or about the same coefficient ofthermal expansion as that of the back substrate.

Electrodes 12 are strips of conductive material. Typically, theelectrodes are Cu, Al, or a silver-containing conductive frit. Theelectrodes can also be a transparent conductive oxide material, such asindium tin oxide, especially in cases where it is desirable to have atransparent display panel. The electrodes are patterned on backsubstrate 10, usually forming parallel strips spaced about 120 μm to 360μm apart, having widths of about 50 μm to 75 μm, thicknesses of about 2μm to 15 μm, and lengths that span the entire active display area whichcan range from a few centimeters to several tens of centimeters.

Barrier ribs 14 contain ceramic particles which have been fused orsintered by firing to form rigid, substantially dense, dielectricbarrier ribs. The ceramic material of the barrier ribs is preferablyalkali-metal free. The presence of alkali metals in the glass frit orceramic powder can lead to undesirable migration of conductive materialfrom the electrodes on the substrate. The ceramic material forming thebarrier ribs has a softening temperature lower than the softeningtemperature of the substrate. The softening temperature is the lowesttemperature at which a glass or ceramic material can be fused to arelatively dense structure having little or no surface-connect porosity.Preferably, the softening temperature of the ceramic material of theslurry is less than about 600° C., more preferably less than about 560°C., and most preferably less than about 500° C. Preferably, the materialof the barrier ribs has a coefficient of thermal expansion that iswithin 10% of the coefficient of expansion of the glass substrates.Close matching of the coefficients of expansion of the barrier ribs andthe substrates reduces the chances of damaging the ribs duringprocessing. Also, differences in coefficients of thermal expansion cancause significant substrate warpage or breakage. Barrier ribs in PDPstypically have heights of about 120 μm to 140 μm and widths of about 20μm to 75 μm. The pitch (number per unit length) of the barrier ribspreferably matches the pitch of the electrodes.

It is important that PDP barrier ribs be positioned on the substratebetween electrode positions. In other words, the pitch, or theperiodicity, of the barrier ribs should closely match the pitch of theelectrodes across the entire width of the display area. Misalignmentadversely affects the functionality of the display. The spacing betweenthe peaks of adjacent barrier ribs is preferably held to a tolerance oftens of parts per million (ppm) of the electrode pitch over the entirewidth of the display. Because the larger displays can have widths of 100cm or more with an electrode pitch of about 200 μm, the barrier ribs arepreferably patterned to hold their alignment with the electrodes towithin 10 μm to 40 μm over nearly 100 cm.

While it is the phosphors and not the barrier ribs that give off visiblelight in an active display, the optical properties of the ribs canenhance or detract from the display characteristics. Preferably, thesides of the barrier ribs are white and highly reflective so that lightwhich does not directly exit an activated cell is not lost to absorptionin significant amounts.

The barrier ribs also preferably have a low porosity. Highly porous ribshave large surface areas that can trap molecules which may contaminatethe display and decrease the life of the display. When the displaysubstrates are put together and sealed, the air between the substrateelements is replaced with an inert gas mixture for plasma generation.Molecules adsorbed in porous ribs can remain inside the display anddesorb over time, leading to contamination and reducing the lifetime ofthe display.

After forming and firing the barrier rib materials, the phosphormaterials are deposited between the barrier ribs, typically by screenprinting. For linear barrier ribs, one type of phosphor material isdeposited along the entire length of each channel defined by an adjacentpair of barrier ribs. The type of phosphor is alternated for adjacentchannels to form a repeating pattern such as red, green, blue, red,green, blue, and so on.

The process of the present invention permits forming and aligningmicrostructures on a patterned substrate. The process of the presentinvention involves providing a mold, providing a material which can becured or hardened to form microstructures, placing the material betweenthe mold and a patterned substrate, aligning the mold with the patternof the substrate, hardening the material between the mold and thesubstrate, and removing the mold. The mold has two opposing majorsurfaces, a generally flat surface and a patterned, or structured,surface. The patterned surface of the mold has a plurality ofmicrostructures which represent the negative image of themicrostructures to be formed and aligned on the patterned substrate. Asdescribed in further detail below, the pattern of the mold is designedsuch that matching between the pattern of the mold and the pattern ofthe substrate can be achieved by stretching the mold in at least onedirection. By so stretching the mold for alignment, the mold can becorrected for mold or substrate variations due to variations inprocessing conditions, variations in the environment (such astemperature and humidity changes), and aging which can cause slightshifting, elongation, or shrinking of the pattern of the mold. If theposition of the mold shifts in any manner during processing, themicrostructures being formed on the substrate can become damaged and/ormisaligned.

In many applications, the microstructures to be formed on the substrateare to be aligned with a patterned portion of the substrate in such amanner that each microstructure is positioned in a precise locationrelative to the pattern of the substrate. For example, on PDP substrateshaving a plurality of parallel electrodes, it is desirable to formuniformly-sized ceramic barriers positioned between each electrode. PDPsubstrates can have 1000 to 5000 or more parallel address electrodesthat must each be separated by barrier ribs. Each of these barrier ribsmust be placed with a certain precision, and this precision must be heldacross the width of the substrate. The process of the present inventionallows for accurate and precise alignment of the mold pattern with thesubstrate pattern to form microstructures on the substrate with accurateand precise alignment which is consistently held across the substrate.

The material for forming the microstructures on the patterned substratecan be placed between the mold and the substrate in a variety of ways.The material can be placed directly in the pattern of the mold followedby placing the mold and material on the substrate, the material can beplaced on the substrate followed by pressing the mold against thematerial on the substrate, or the material can be introduced into a gapbetween the mold and the substrate as the mold and substrate are broughttogether by mechanical or other means. The method used for placing thematerial between the mold and the substrate depends on, among otherthings, the aspect ratio of the structures to be formed on thesubstrate, the viscosity of the microstructure-forming material, and therigidity of the mold. Structures having heights that are large comparedto their widths (high aspect ratio structures) require molds havingrelatively deep indentations. In these cases, depending on the viscosityof the material, it can be difficult to completely fill the indentationsof the mold unless the material is injected into the indentations of themold with some force. In addition, care should be taken to fill theindentations of the mold while minimizing the introduction of bubbles orair pockets in the material.

While placing the material between the mold and the substrate, pressurecan be applied between the substrate and the mold to set a landthickness, L, as in FIG. 2. The land is the material between thesubstrate and the base of the microstructures formed on the substrate.The land thickness can vary depending on the application. If zero landthickness is desired, it may be preferable to fill the mold with thematerial and then remove any excess material from the mold using a bladeor squeegee before contacting the substrate. For other applications, itmay be desirable to have a non-zero land thickness. In the case of PDPs,the material forming the microstructured barrier ribs is a dielectric,and the land thickness determines the thickness of dielectric materialpositioned on substrate electrodes 12. Thus, for PDPs, the landthickness can be important for determining what voltage must be appliedbetween electrodes to generate a plasma and to activate a pictureelement.

The next step is to align the pattern of the mold with the pattern ofthe substrate. Under ideal conditions, the pattern of the mold asfabricated and the pattern of the substrate as fabricated wouldperfectly match. However, in practice this is rarely, if ever, the case.Processing steps can cause the dimensions of the substrate and the moldto change. While these dimensional changes might be slight, they canadversely affect the precise placement of microstructures aligned withthe substrate pattern using a mold. For example, a PDP substrate havinga width of 100 cm and an electrode pitch of 200 μm requires that each of5000 barrier ribs be placed precisely between adjacent electrodes. Adifference between the pitch of the electrodes and the pitch of the moldof only 0.1 μm (or 0.05%) means that the pattern of the barrier ribs andthe electrode pattern on the substrate will be misaligned, and be 180°out of phase in at least two regions across the substrate. This is fatalfor display device functionality. For such a PDP substrate, the pitch ofthe mold and the pitch of the electrodes should have a mismatch of 0.01%or less.

The process of the present invention employs a mold capable of beingstretched to facilitate precise alignment of the pattern of the moldwith the pattern of the substrate. First, the mold is rough aligned byplacing the pattern of the mold in the same orientation as the patternof the substrate. The mold and substrate are checked for registry oftheir respective patterns. The mold is stretched in one or moredirections parallel to the plane of the substrate until the desiredregistry is achieved. In the case of substrates having a pattern ofparallel lines, such as electrodes on a PDP substrate, the mold ispreferably stretched in one direction, either parallel to the substratepattern or perpendicular to the substrate pattern, depending on whetherthe pitch of the mold is greater than or less than the pitch of thesubstrate pattern. FIG. 3 shows the case where mold 30 is stretched in adirection parallel to the parallel line pattern of the substrate 34. Inthis case, the pitch of the pattern of the mold is reduced duringstretching to conform it to the pitch of the pattern of the substrate.To expand the pitch of the mold, the mold is stretched in theperpendicular direction.

Stretching can take place using a variety of known techniques. Forexample, the edges of the mold can be attached to adjustable rollerswhich can increase or decrease the tension on the mold until alignmentis achieved. In cases where it is desirable to stretch the mold in morethan one direction simultaneously, the mold can be heated to thermallyexpand the mold until alignment is achieved.

After alignment of the pattern of the mold with the pattern of thesubstrate, the material between the mold and the substrate is cured toform microstructures adhered to the surface of the substrate. Curing ofthe material can take place in a variety of ways depending on the binderresin used. For example, the material can be cured by curing usingvisible light, ultraviolet light, e-beam radiation, or other forms ofradiation, by heat curing, or by cooling to solidification from a meltedstate. When radiation curing, radiation can be propagated through thesubstrate, through the mold, or through the substrate and the mold.Preferably, the cure system chosen optimizes adhesion of the curedmaterial to the substrate. As such, in cases where material is usedwhich tends to shrink during hardening and radiation curing is used, thematerial is preferably cured by irradiating through the substrate. Ifthe material is cured only through the mold, the material might pullaway from the substrate via shrinkage during curing, thereby adverselyaffecting adhesion to the substrate. In the present application, curablerefers to a material that may be cured as described above.

After curing the material to form microstructures adhered to thesubstrate surface and aligned to the pattern of the substrate, the moldcan be removed. Providing a stretchable and flexible mold can aid inmold removal because the mold can be peeled back so that the demoldingforce can be focused on a smaller surface area. As shown in FIG. 4, whenlinear rib-like microstructures are molded such as barrier ribs 24, mold30 is preferably removed by peeling back along a direction parallel withribs 24 and mold pattern 34. This minimizes the pressure appliedperpendicular to the ribs during mold removal, thereby reducing thepossibility of damaging the ribs. Preferably, a mold release is includedeither as a coating on the patterned surface of the mold or in thematerial that is hardened to form the microstructure itself. Theadvantages of including a mold release composition in the hardenablematerial is described in more detail below with respect to a moldableslurry used to form ceramic barrier ribs on a PDP substrate. A moldrelease material becomes more important as higher aspect ratiostructures are formed. Higher aspect ratio structures make demoldingmore difficult, and can lead to damage to the microstructures. Asdiscussed above, curing the material from the substrate side not onlyhelps improve adhesion of the hardened microstructures to the substrate,but can allow the structures to shrink toward the substrate duringcuring, thereby pulling away from the mold to permit easier demolding.

After the mold is removed, what remains is the patterned substratehaving a plurality of hardened microstructures adhered thereon andaligned with the pattern of the substrate. Depending on the application,this can be the finished product. In other applications such assubstrates that will have a plurality of ceramic microstructures, thehardened material contains a binder which is preferably removed bydebinding at elevated temperatures. After debinding, or burning out ofthe binder, firing of the green state ceramic microstructures isperformed to fuse the glass particles or sinter the ceramic particles inthe material of the microstructures. This increases the strength andrigidity of the microstructures. Shrinkage also occurs during firing asthe microstructure densifies. FIG. 5 shows ceramic microstructures 14after firing on a substrate 10 having patterned electrodes 12. Firingdensifies microstructures 14 so that their profile shrinks somewhat fromtheir green state profile 24 as indicated. As shown, firedmicrostructures 14 maintain their positions and their pitch according tothe substrate pattern.

For PDP display applications, phosphor material is applied to firedbarrier ribs, and the substrate can then be installed into a displayassembly. This involves aligning a front substrate having sustainelectrodes with the back substrate having address electrodes, barrierribs, and phosphor such that the sustain electrodes are perpendicularwith the address electrodes. The areas through which the opposingelectrodes cross define the pixels of the display. The space between thesubstrates is then evacuated and filled with an inert gas as thesubstrates are bonded together and sealed at their edges.

It should be noted that the process of the present invention can lenditself well to automation to take advantage of the efficiencies offeredby continuous processing. For example, the patterned substrate can beconveyed by a belt or other mechanisms to an area where the mold can bebrought into close proximity with the substrate by, for example, arotating drum. As the mold is brought close to the substrate, anextrusion die or other means can be used to apply the curable slurrybetween the patterned surface of the mold and the patterned surface ofthe substrate. The conveyer means for the substrate and the conveyermeans for the mold are positioned such that rough positioning of thepattern of the mold with the pattern of the substrate occurs as the twoare brought together and as the material is placed therebetween. Afterplacing the hardenable material between the substrate and the mold,alignment between the pattern of the mold and the pattern of thesubstrate can be automatically checked, for example by opticaldetectors. The optical detectors can look for alignment fiducials orcheck for a moire interference pattern due to misalignment of thepattern of the mold and the pattern of the substrate. The mold can thenbe stretched by, for example, gripping a pair of opposing edges of themold and pulling until the optical detectors confirm alignment. At thispoint, the material between the mold and substrate can be cured byirradiating the material through the substrate, through the mold, orboth. After a predetermined curing time, the substrate and mold can beadvanced as the rotating drum peels the mold away from the curedmicrostructures formed and aligned on the patterned substrate.

FIG. 6 shows an apparatus for molding, aligning, and curingmicrostructures on a patterned substrate using a microstructured mold.Substrate 84 resides on mechanical stage 92 which preferably has theability of x-motion (motion from left to right in the figure), y-motion(motion in and out of the page of the figure), and θ-motion (rotationalmotion in the x-y plane). Such motion allows substrate 84 to be movedinto position for alignment and curing, to be rough aligned with themold, and to be moved out of position for removal of the mold aftercuring. Rolls 90 a and 90 b are wind up and unwind rolls, respectively,for moving flexible, stretchable mold 80 in line with substrate 84. Tointroduce the curable material between substrate 84 and mold 80,substrate 84 and mold 80 are moved in concert as the curable material isinjected by injection means 98 into a gap between mold 80 and substrate84 near roll 88 a. Substrate 84 and mold 80 are moved in unison as thematerial is applied therebetween until the desired amount of material isapplied between the pattern of the substrate and the pattern of themold. FIG. 6 shows the substrate 84 and mold 80, having curable material82 disposed between, moved into an area where optical detectors 96 a and96 b check for alignment. Depending on the pattern of themicrostructures, two or more detectors may be required. Rollers 88 a and88 b can then be oppositely rotated to stretch the mold until thepattern of the mold and the pattern of the substrate are aligned withthe desired precision. At this point, radiation source 94 is used toirradiate curable material 82 through substrate 84. After material 82 iscured, the substrate and mold are moved in unison as roller 88 b acts topeel the mold away from the cured microstructures which have been moldedin alignment with the pattern of the substrate.

An alternative method of molding and aligning microstructures on apatterned substrate according to the present invention involves a staticstretching method. For example, a patterned substrate can be providedwhich has protrusions or indentions located outside of the pattern ofthe substrate and on opposing ends of the substrate. The stretchablemold also has protrusions or indentions located outside of themicrostructured pattern of the mold which align and interlock with thoseprovided on the substrate when the mold is slightly stretched. Theseadded interlocking features on the substrate and the mold hold thepattern of the mold in alignment with the pattern of the substratewithout the need for other machinery.

The method of the present invention preferably uses a mold capable ofbeing stretched in at least one direction to align the pattern of themold to a predetermined portion of the patterned substrate. The mold ispreferably a flexible polymer sheet having a smooth surface and anopposing microstructured surface. The mold can be made by compressionmolding of a thermoplastic material using a master tool which has amicrostructured pattern. The mold can also be made of a curable materialwhich is cast and cured onto a thin, flexible polymer film.

The microstructured mold of the present invention is preferably formedaccording to a process similar to the processes disclosed in U.S. Pat.No. 5,175,030 (Lu et al.) and U.S. Pat. No. 5,183,597 (Lu). Theformation process preferably includes the following steps: (a) preparingan oligomeric resin composition; (b) depositing the oligomeric resincomposition onto a master negative microstructured tooling surface in anamount barely sufficient to fill the cavities of the master; (c) fillingthe cavities by moving a bead of the composition between a preformedsubstrate and the master, at least one of which is flexible; and (d)curing the oligomeric composition.

The oligomeric resin composition of step (a) preferably is a one-part,solvent-free, radiation-polymerizable, crosslinkable, organic oligomericcomposition. The oligomeric composition is preferably one which iscurable to form a flexible and dimensionally-stable cured polymer. Thecuring of the oligomeric resin should occur with low shrinkage. Onepreferred suitable oligomeric composition is an aliphatic urethaneacrylate such as one sold by the Henkel Corporation, Ambler, Pa., underthe trade designation Photomer 6010, although similar compounds areavailable from other suppliers.

Acrylate functional monomers and oligomers are preferred because theypolymerize more quickly under normal curing conditions. Further, a largevariety of acrylate esters are commercially available. However,methacrylate, acrylamide and methacrylamide functional ingredients canalso be used without restriction. Herein, where acrylate is used,methacrylate is understood as being acceptable.

Polymerization can be accomplished by usual means, such as heating inthe presence of free radical initiators, irradiation with ultraviolet orvisible light in the presence of suitable photoinitiators, and byirradiation with electron beam. For reasons of convenience, low capitalinvestment, and production speed, the preferred method of polymerizationis by irradiation with ultraviolet or visible light in the presence ofphotoinitiator at a concentration of about 0.1 percent to about 1.0percent by weight of the oligomeric composition. Higher concentrationscan be used but are not normally needed to obtain the desired curedresin properties.

The viscosity of the oligomeric composition deposited in step (b) ispreferably between 500 and 5000 centipoise (500 and 5000×10⁻³Pascal-seconds). If the oligomeric composition has a viscosity abovethis range, air bubbles might become entrapped in the composition.Additionally, the composition might not completely fill the cavities inthe master tooling. For this reason, the resin can be heated to lowerthe viscosity into the desired range. When an oligomeric compositionwith a viscosity below that range is used, the oligomeric compositionusually experiences shrinkage upon curing that prevents the oligomericcomposition from accurately replicating the master.

Almost any material can be used for the base (substrate) of thepatterned mold, as long as that material is substantially opticallyclear to the curing radiation and has enough strength to allow handlingduring casting of the microstructure. In addition, the material used forthe base should be chosen so that it has sufficient thermal stabilityduring processing and use of the mold. Polyethylene terephthalate orpolycarbonate films are preferable for use as a substrate in step (c)because the materials are economical, optically transparent to curingradiation, and have good tensile strength. Substrate thicknesses of0.025 millimeters to 0.5 millimeters are preferred and thicknesses of0.075 millimeters to 0.175 millimeters are especially preferred. Otheruseful substrates for the microstructured mold include cellulose acetatebutyrate, cellulose acetate propionate, polyether sulfone, polymethylmethacrylate, polyurethane, polyester, and polyvinyl chloride. Thesurface of the substrate may also be treated to promote adhesion to theoligomeric composition.

Examples of such polyethylene terephthalate based materials include:photograde polyethylene terephthalate; and polyethylene terephthalate(PET) having a surface that is formed according to the method describedin U.S. Pat. No. 4,340,276.

A preferred master for use with the above-described method is a metallictool. If the temperature of the curing and optionally simultaneous heattreating step is not too great, the master can also be constructed froma thermoplastic material, such as a laminate of polyethylene andpolypropylene.

After the oligomeric resin fills the cavities between the substrate andthe master, the oligomeric resin is cured, removed from the master, andmay or may not be heat treated to relieve any residual stresses. Whencuring of the mold resin material results in shrinkage of greater thanabout 5% (e.g., when a resin having a substantial portion of monomer orlow molecular weight oligomers is used), it has been observed that theresulting microstructures can be distorted. The distortion that occursis typically evidenced by a concave microstructure sidewalls and/orslanted tops on features of the microstructures. Although these lowviscosity resins perform well for replication of small, low aspect ratiomicrostructures, they are not preferred for relatively high aspect ratiomicrostructures for which the sidewall angles and the top flatness mustbe maintained. In forming ceramic barrier ribs for PDP applications,relatively high aspect ratio ribs are desired, and the maintenance ofrelatively straight sidewalls and tops on the barrier ribs can beimportant.

As indicated above, the mold can alternatively be replicated bycompression molding a suitable thermoplastic against the master metaltool.

When using the method of the present invention to mold and align ceramicmicrostructures on patterned display substrates, the molding material ispreferably a slurry containing a mixture of at least three components.The first component is a ceramic powder. The ceramic material of theslurry will ultimately be fused or sintered by firing to formmicrostructures having desired physical properties adhered to thepatterned substrate. The second component is a fugitive binder which iscapable of being shaped and subsequently hardened by curing or cooling.The binder allows the slurry to be shaped into semi-rigid green statemicrostructures which are adhered to the substrate so that thestretchable mold used to form and align the microstructures can beremoved in preparation for debinding and firing. The third component isa diluent which can promote release from the mold after alignment andhardening of the binder material, and can promote fast and complete burnout of the binder during debinding before firing the ceramic material ofthe microstructures. The diluent preferably remains a liquid after thebinder is hardened so that the diluent phase-separates from the bindermaterial during binder hardening.

The ceramic powder is chosen based on the end application of themicrostructures and the properties of the substrate to which themicrostructures will be adhered. One consideration is the coefficient ofthermal expansion (CTE) of the substrate material. Preferably, the CTEof the ceramic material of the slurry differs from the CTE of thesubstrate material by no more than about 10%. When the substratematerial has a CTE which is much less than or much greater than the CTEof the ceramic material of the microstructures, the microstructures canwarp, crack, fracture, shift position, or completely break off from thesubstrate during processing or use. Further, the substrate can warp dueto a high difference in CTE between the substrate and the ceramicmicrostructures.

The substrate should be able to withstand the temperatures necessary toprocess the ceramic material of the slurry. Glass or ceramic materialssuitable for use in the slurry preferably have softening temperaturesbelow about 600° C., and usually between about 400° C. and 600° C. Thus,a preferred choice for the substrate is a glass, ceramic, metal, orother rigid material which has a softening temperature which is higherthan that of the ceramic material of the slurry. Preferably, thesubstrate has a softening temperature which is higher than thetemperature at which the microstructures are to be fired. In addition,glass or ceramic materials suitable for use in the slurry of the presentinvention preferably have coefficients of thermal expansion of about5×10⁻⁶/° C. to 13×10⁻⁶/° C. Thus, the substrate preferably has a CTEapproximately in this range as well.

Choosing a ceramic powder having a low softening temperature allows theuse of a substrate also having a relatively low softening temperature.In the case of glass substrates, soda lime float glass having lowsoftening temperatures is typically less expensive than glass havinghigher softening temperatures. Thus, the use of a low softeningtemperature ceramic powder can allow the use of a less expensive glasssubstrate. In addition, low softening temperature ceramic materials inthe slurry of the present invention can make high precisionmicrostructures easier to obtain. For example, when fabricating barrierribs on a PDP glass substrate, the precision and accuracy in thealignment and placement of the barrier ribs with respect to theelectrodes on the substrate should be maintained throughout processing.The ability to fire green state barrier ribs at lower temperaturesminimizes the thermal expansion and the amount of stress relief requiredduring heating, thus avoiding undue substrate distortion, barrier ribwarping, and barrier rib delamination.

Lower softening temperature ceramic materials can be obtained byincorporating certain amounts of alkali metals, lead, or bismuth intothe material. However, for PDP barrier ribs, the presence of alkalimetals in the microstructured barriers can cause material from theelectrodes to migrate across the substrate during elevated temperatureprocessing. The diffusion of electrode material can cause interference,or “crosstalk”, as well as shorts between adjacent electrodes, degradingdevice performance. Thus, for PDP applications, the ceramic powder ofthe slurry is preferably substantially free of alkali metal. Inaddition, the incorporation of lead or bismuth in the ceramic materialof the slurry can make environmentally-friendly disposal of the materialproblematic. When the incorporation of lead or bismuth is not desirable,low softening temperature ceramic material can be obtained usingphosphate or B₂O₃-containing compositions. One such composition includesZnO and B₂O₃. Another such composition includes BaO and B₂O₃. Anothersuch composition includes ZnO, BaO, and B₂O₃. Another such compositionincludes La₂O₃ and B₂O₃. Another such composition includes Al₂O₃, ZnO,and P₂O₅.

Other fully soluble, insoluble, or partially soluble components can beincorporated into the ceramic material of the slurry to attain or modifyvarious properties. For example, Al₂O₃ or La₂O₃ can be added to increasechemical durability of the composition and decrease corrosion. MgO canbe added to increase the glass transition temperature or to increase theCTE of the composition. TiO₂ can be added to give the ceramic material ahigher degree of optical opacity, whiteness, and reflectivity. Othercomponents or metal oxides can be added to modify and tailor otherproperties of the ceramic material such as the CTE, softeningtemperature, optical properties, physical properties such asbrittleness, and so on.

Other means of preparing a composition which can be fired at relativelylow temperatures include coating core particles in the composition witha layer of low temperature fusing material. Examples of suitable coreparticles include ZrO₂, Al₂O₃, ZrO₂—SiO₂, and TiO₂. Examples of suitablelow fusing temperature coating materials include B₂O₃, P₂O₅, and glassesbased on one or more of B₂O₃, P₂O₅, and SiO₂. These coatings can beapplied by various methods. A preferred method is a sol-gel process inwhich the core particles are dispersed in a wet chemical precursor ofthe coating material. The mixture is then dried and comminuted (ifnecessary) to separate the coated particles. These particles can bedispersed in the glass or ceramic powder of the slurry or can be used bythemselves for the glass powder of the slurry.

The ceramic powder in the slurry which can be used in the method of thepresent invention is preferably provided in the form of particles whichare dispersed throughout the slurry. The preferred size of the particlesdepends on the size of the microstructures to be formed and aligned onthe patterned substrate. Preferably, the average size, or diameter, ofthe particles in the ceramic powder of the slurry is no larger thanabout 10% to 15% the size of the smallest characteristic dimension ofinterest of the microstructures to be formed and aligned. For example,PDP barrier ribs can have widths of about 20 μm, and their widths arethe smallest feature dimension of interest. For PDP barrier ribs of thissize, the average particle size in the ceramic powder is preferably nolarger than about 2 or 3 μm. By using particles of this size or smaller,it is more likely that the microstructures will be replicated with thedesired fidelity and that the surfaces of the ceramic microstructureswill be relatively smooth. As the average particle size approaches thesize of the microstructures, the slurry containing the particles may nolonger conform to the microstructured profile. In addition, the maximumsurface roughness can vary based in part on the ceramic particle size.Thus, it is easier to form smoother structures using smaller particles.

The fugitive binder of the slurry is an organic binder chosen based onfactors such as its ability to bind to the ceramic powder of the slurry,ability of being cured or otherwise hardened to retain a moldedmicrostructure, ability of adhering to the patterned substrate, andability to volatilize (or burn out) at temperatures at least somewhatlower than those used for firing the green state microstructures. Thebinder helps bind together the particles of the ceramic powder when thebinder is cured or hardened so that the stretchable mold can be removedto leave rigid green state microstructures adhered to and aligned withthe patterned substrate. The binder is referred to as a “fugitivebinder” because the binder material can be burned out of themicrostructures at elevated temperatures prior to fusing or sinteringthe ceramic particles in the microstructures. Preferably, firingcompletely burns out the fugitive binder so that the microstructuresleft on the patterned surface of the substrate are fused glass orceramic microstructures which are substantially free of carbon residue.In applications where the microstructures used are dielectric barriers,such as in PDPs, the binder is preferably a material capable ofdebinding at a temperature at least somewhat below the temperaturedesired for firing without leaving behind a significant amount of carbonwhich can degrade the dielectric properties of the microstructuredbarriers. For example, binder materials containing a significantproportion of aromatic hydrocarbons, such as phenolic resin materials,can leave graphitic carbon particles during debinding which can requiresignificantly higher temperatures to completely remove.

The binder is preferably an organic material which is radiation or heatcurable. Preferred classes of materials include acrylates and epoxies.Alternatively, the binder can be a thermoplastic material which isheated to a liquid state to conform to the mold and then cooled to ahardened state to form microstructures adhered to the substrate. Whenprecise placement and alignment of the microstructures on the substrateis desired, it is preferable that the binder is radiation curable sothat the binder can be hardened under isothermal conditions. Underisothermal conditions (no change in temperature), the stretchable mold,and therefore the slurry in the mold, can be held in a fixed positionrelative to the pattern of the substrate during hardening of the bindermaterial. This reduces the risk of shifting or expansion of the mold orthe substrate, especially due to differential thermal expansioncharacteristics of the mold and the substrate, so that precise placementand alignment of the mold can be maintained as the slurry is hardened.

When using a fugitive binder which is radiation curable, it ispreferable to use a cure initiator that is activated by radiation towhich the substrate is substantially transparent so that the slurry canbe cured by exposure through the substrate. For example, when thesubstrate is glass, the fugitive binder is preferably visible lightcurable. By curing the binder through the substrate, the slurry materialadheres to the substrate first, and any shrinkage of the binder materialduring curing will tend to occur away from the mold and toward thesurface of the substrate. This helps the microstructures demold andhelps maintain the location and accuracy of the microstructure placementon the pattern of the substrate.

In addition, the selection of a cure initiator can depend on whatmaterials are used for the ceramic powder in the slurry used in thepresent invention. For example, in applications where it is desirable toform ceramic microstructures which are opaque and highly diffuselyreflective, it can be advantageous to include a certain amount oftitania (TiO₂) in the ceramic powder of the slurry. While titania can beuseful for increasing the reflectivity of the microstructures, it canalso make curing with visible light difficult because visible lightreflection by the titania in the slurry can prevent sufficientabsorption of the light by the cure initiator to effectively cure thebinder. However, by selecting a cure initiator which is activated byradiation which can simultaneously propagate through the substrate andthe titania particles, effective curing of the binder can take place.One example of such a cure initiator isbis(2,4,6-trimethylbenzoyl)phenylphosphineoxide, a photoinitiatorcommercially available from Ciba Specialty Chemicals, Hawthrone, N.Y.,under the trade designation Irgacure 819. Another example is a ternaryphotoinitiator system prepared such as those described in U.S. Pat. No.5,545,670 such as a mixture of ethyl dimethylaminobenzoate,camphoroquinone, and diphenyl iodonium hexafluorophosphate. Both ofthese examples are active in the blue region of the visible spectrumnear the edge of the ultraviolet in a relatively narrow region where theradiation can penetrate both a glass substrate and titania particles inthe slurry. Other cure systems may be selected for use in the process ofthe present invention based on the binder, the materials of the ceramicpowder in the slurry, and the material of the mold or the substratethrough which curing is to take place.

The diluent of the slurry used in the method of the present invention isa material selected based on factors such as its ability to enhance moldrelease properties of the slurry subsequent to curing the fugitivebinder and to enhance debinding properties of green state structuresmade using the slurry. The diluent is preferably a material that issoluble in the binder prior to curing and which remains liquid aftercuring the fugitive binder. This provides two advantages. First, byremaining a liquid when the binder is hardened, the diluent reduces therisk of the cured binder material adhering to the mold. Second, byremaining a liquid when the binder is hardened, the diluent phaseseparates from the binder material, thereby forming an interpenetratingnetwork of small pockets, or droplets, of diluent dispersed throughoutthe cured binder matrix. The advantages of phase separation of thediluent will become clear in the discussion that follows.

For many applications, such as PDP barrier ribs, it is desirable fordebinding of the green state microstructures to be substantiallycomplete before firing. Additionally, debinding is often the longest andhighest temperature step in thermal processing. Thus, it is desirablefor the slurry to be capable of debinding relatively quickly andcompletely and at a relatively low temperature. The preference for lowtemperatures is discussed in detail below.

While not wishing to be bound by any theory, debinding can be thought ofas being kinetically and thermodynamically limited by twotemperature-dependent processes, namely diffusion and volatilization.Volatilization is the process by which decomposed binder moleculesevaporate from a surface of the green state structures and thus leave aporous network for resin egress to proceed in a less obstructed manner.In a single phase resin binder, internally-trapped gaseous degradationproducts can blister and/or rupture the structure. This is moreprevalent in binder systems that leave a high level of carbonaceousdegradation products at the surface which can form an impervious skinlayer to stop the egress of binder degradation gases. In cases wheresingle phase binders are successful, the cross sectional area isrelatively small and the binder degradation heating rate is inherentlylong to prevent a skin layer from forming.

The rate at which volatilization occurs depends on temperature, anactivation energy for volatilization, and a frequency, or sampling rate.Because volatilization occurs primarily at or near surfaces, thesampling rate is proportional to the total surface area of thestructures. Diffusion is the process by which binder molecules migrateto surfaces from the bulk of the structures. Due to volatilization ofbinder material from the surfaces, there is a concentration gradientwhich tends to drive binder material toward the surfaces where there isa lower concentration. The rate of diffusion depends on temperature, anactivation energy for diffusion, and a frequency.

Because volatilization is limited by the surface area, if the surfacearea is small relative to the bulk of the microstructures, heating tooquickly can cause volatile species to be trapped. When the internalpressure gets large enough, the structures can bloat, break or fracture.To curtail this effect, debinding can be accomplished by a relativelygradual increase in temperature until debinding is complete. A lack ofopen channels for debinding, or debinding too quickly, can also lead toa higher tendency for residual carbon formation. This in turn requireshigher debinding temperatures to ensure complete debinding. Whendebinding is complete, the temperature can be ramped up more quickly tothe firing temperature and held at that temperature until firing iscomplete. At this point, the articles can then be cooled.

The diluent enhances debinding by providing shorter pathways fordiffusion and increased surface area. The diluent preferably remains aliquid and phase separates from the fugitive binder when the binder iscured or otherwise hardened. This creates an interpenetrating network ofpockets of diluent dispersed in a matrix of hardened binder material.The faster that curing or hardening of the binder material occurs, thesmaller the pockets of diluent will be. Preferably, after hardening thebinder, a relatively large amount of relatively small pockets of diluentwill be dispersed in a network throughout the green state structures.During debinding, the low molecular weight diluent can evaporate quicklyat relatively low temperatures prior to decomposition of the other highmolecular weight organic components. Evaporation of the diluent leavesbehind a somewhat porous structure, thereby greatly increasing thesurface area from which remaining binder material can volatilize andgreatly decreasing the mean path length over which binder material mustdiffuse to reach these surfaces. Therefore, by including the diluent,the rate of volatilization during binder decomposition is increased byincreasing the available surface area, thereby increasing the rate ofvolatilization for the same temperatures. This makes pressure build updue to limited diffusion rates less likely to occur. Furthermore, therelatively porous structure allows pressures that are built up to bereleased easier and at lower thresholds. The result is that debindingcan be performed at a faster rate of temperature increase whilelessening the risk of microstructure breakage. In addition, because ofthe increased surface area and decreased diffusion length, debinding iscomplete at a lower temperature.

The diluent is not simply a solvent compound for the resin. The diluentis preferably soluble enough to be incorporated into the resin mixturein the uncured state. Upon curing of the binder of the slurry, thediluent should phase separate from the monomers and/or oligomersparticipating in the cross-linking process. Preferably, the diluentphase separates to form discrete pockets of liquid material in acontinuous matrix of cured resin, with the cured resin binding theparticles of the glass frit or ceramic powder of the slurry. In thisway, the physical integrity of the cured green state microstructures isnot greatly compromised even when appreciably high levels of diluent areused (i.e., greater than about a 1:3 diluent to resin ratio).

Preferably the diluent has a lower affinity for bonding with the ceramicpowder material of the slurry than the affinity for bonding of thebinder material with the ceramic powder. When hardened, the bindershould bond with the particles of the ceramic powder. This increases thestructural integrity of the green state structures, especially afterevaporation of the diluent. Other desired properties for the diluentwill depend on the choice of ceramic powder, the choice of bindermaterial, the choice of cure initiator (if any), the choice of thesubstrate, and other additives (if any). Preferred classes of diluentsinclude glycols and polyhydroxyls, examples of which includebutanediols, ethylene glycols, and other polyols.

In addition to ceramic powder, fugitive binder, and diluent, the slurrycan optionally include other materials. For example, the slurry caninclude an adhesion promoter to promote adhesion to the substrate. Forglass substrates, or other substrates having silicon oxide or metaloxide surfaces, a silane coupling agent is a preferred choice as anadhesion promoter. A preferred silane coupling agent is a silanecoupling agent having three alkoxy groups. Such a silane can optionallybe pre-hydrolyzed for promoting better adhesion to glass substrates. Aparticularly preferred silane coupling agent is a silano primer such assold by Manufacturing Co. (3M), St. Paul, Minn. under the tradedesignation Scotchbond Ceramic Primer. Other optional additives caninclude materials such as dispersants which aid in mixing the ceramicpowder with the other components of the slurry of the present invention.Optional additives can also include surfactants, catalysts, anti-agingcomponents, release enhancers, and so on.

PDP substrates are typically soda lime glass material made by floatglass processing methods. Although conventional soda lime glass iswidely available at low cost, the softening temperature of such glassmaterial has been too low for conventional PDP processing temperatures.Glass substrates for PDP applications are typically compositionallymodified to raise the softening temperature. Often, this entailsreducing the level of alkali material and increasing the level ofalumina in the glass. The cost of soda lime glass so modified issignificantly more than unmodified soda lime float glass material.

The highest processing temperature in PDP manufacturing occurs duringbarrier rib fabrication. With current manufacturing processes,processing temperatures greater than 560° C. are required to ensure thatbarrier rib materials are dense and are free of residual carbon.Although lower temperature fusing glass materials are available, the useof such materials can be prohibitive because the binder burn outtemperatures are excessive. An important advantage of the method of thepresent invention is its use of relatively low ceramic microstructureprocessing temperatures, thus enabling use of low cost unmodified sodalime glass.

Electrodes can be applied on a PDP back substrate by a variety ofmethods including thin-film and thick film methods. Thin film methodsinvolve physical vapor deposition of metal materials, typically Cr/Cu/Cror Al, followed by lithography and etching to define the desiredpattern. Thin film electrodes are usually less than 2 μm in thickness.Thick film method involves screen printing a silver frit material,firing to remove organic vehicles and fusing to enhance conductivity. Abase alkali-free dielectric layer is also required with the thick filmprocess since silver migration can occur on soda lime glass substrates.Thick film electrodes are typically 5 to 15 μm in thickness.

The present invention will now be illustrated by the followingnon-limiting examples.

EXAMPLES Examples 1 and 2

In the examples which follow, a jig was built to stretch a sheet of apolymer mold as shown in FIG. 7. To stretch a sheet of a polymer mold,S, the sheet was gripped at points A and B. Lateral force (in the planeof the mold) was then applied by turning a fine thread screw, C. The jigwas designed to fit under a toolmaker microscope to observe the patternof the polymer tool while stretching. Polymer mold pitch measurementswere taken at various strain levels. Free-state pitch measurements weremade before and after stretching to determine whether the levels ofstrain applied had caused plastic or elastic deformation. The polymermolds were about 2.5 cm wide and about 15 cm long.

Example 1

A polymer mold with V-groove microstructures was used. The polymer moldwas a flat PET film onto which an acrylate material was cast and curedto form V-groove microstructures. The PET film was nominally 127 μmthick and the microstructure bearing acrylate layer was about 27 to 30μm thick. In the free state, the V-groove structures were measured to be49.556 μm apart from peak to peak.

As described above, the polymer mold was secured onto the jig to stretchin a direction parallel to the V-grooves. The V-groove spacing, orpitch, was measured at various levels of strain by visual inspectionunder a toolmaker microscope at 200× magnification. The results aresummarized in Table 1. Loading conditions were indicated by the numberof turns of screw C.

TABLE 1 Loading condition Pitch (μm) free state 49.556 pre-load (0turns) 49.530 0.25 49.520 0.50 49.510 0.75 49.500 1.00 49.483 1.2549.470 1.50 49.463 post-load (0 turns) 49.530

The spacing of the microstructured grooves was affected by nearly 1900ppm (parts per million) without any observed permanent deformation(i.e., the loading history was strictly elastic). This range of controldemonstrates the ability to accurately adjust patterned microstructuresfor alignment with a patterned substrate.

Example 2

The same procedure as in Example 1 was repeated for a polymer moldhaving a different construction and a different pattern. In thisexample, the mold had rectangular channels and was a monolithicstructure made entirely of polycarbonate, one surface of which wassmooth and the other surface of which had the rectangular channels. Theentire mold was 550 μm thick and the channels were 198 μm deep. Thechannels were nominally 120 μm in width and were spaced 219.94 μm apart.S strain was applied parallel to the channels in the plane of thepolymer tool. The pitch measurements are summarized in Table 2.

TABLE 2 Strain (%) Pitch (μm) pre-load (0%) 219.87 0.161 219.74 0.342219.59 0.491 219.45 post-load (0%) 219.87

Similarly to Example 1, fine control of the feature pitch spacing wasdemonstrated by controlled stretching of the polymer mold. Again, asmuch as 1900 ppm of shrinkage in the pitch of the channels was obtainedby elastically stretching the mold. Furthermore, the pitch of themicrostructured channels was uniform along a significant portion (about25% of the width) of the length of the polymer mold. By designing apolymer mold having a pattern that does not extend into the region nearthe loading points (where the film is gripped), there will beessentially no non-uniformities introduced into the mold pattern bystretching. Thus, the spacing of the pattern of the mold can be affectedby stretching by the same amount at each point of the pattern.

Examples 3-7

Various concentrations of diluent in a slurry were investigated forbenefits of mold release and debinding rate. The molds used werepolycarbonate or photo-curable acrylate material that was cast and curedonto a high stiffness backing material such as PET. The cast and curedpolycarbonate or acrylate material formed the patterned surface of themold. Cure shrinkage of the slurry and chemical interaction between theslurry and the polymer mold can cause difficulty with demolding. Bondingbetween the slurry and mold can result in longer processing times,fracturing of the cured microstructures, or mold failure. Enhancing thedemolding characteristics is desirable to improve molding yield and toprolong the life of the mold as well as to yield higher fidelityreplicated structures. For PDP barrier rib manufacturing, the ability toquickly fire the ribs is desirable to reduce cycle time and cost. Thebinder must debind, or burn out, quickly and completely to achieve fastfiring. Proper design and incorporation of a diluent component into theslurry of the present invention can enhance both demolding anddebinding.

A photocurable resin active in the visible light region was used as thebinder in preparing the slurry samples in Examples 3-7. Glass frit wasused as the glass powder of the slurry. The glass frit was a leadborosilicate glass powder as commercially available from Asahi Glass Co.under the trade designation RFW030, and had an average particle size of1.2 μm. The base resin was composed of 50% by weight bisphenol-adiglycidyl ether dimethacrylate (BISGMA) and 50% by weight triethyleneglycol dimethacrylate (TEGDMA). An initiator system which allows curingusing visible light in the blue region of the spectrum was used and wascomposed of ethyl dimethylaminobenzoate, camphoroquinone, and diphenyliodonium hexafluorophosphate. The initiator level was kept at 2% byweight of the organic components for all the samples. Glass frit loadingin all the slurries were about 45% to 47% by volume. A phospate esterdispersant was used to help incorporation of the glass frit into theorganic components. Curing was performed using a blue light (380-470 nm)source irradiated through the glass substrate used. Dosage was between 1to 1.5 J/cm². The diluent selected for Examples 3-7 was 1,3 butanediol.1,3 butanediol is not soluble in the BISGMA alone, but is soluble in theBISGMA/TEGDMA mixture. The diluent content in percentage by weight ofthe organic components was as shown in Table 3.

TABLE 3 Example Diluent (% by weight) 3 10 4 20 5 30 6 35 7 40

Debinding Properties

To study effects on binder burn out, thick films of the slurry accordingto Examples 3-7 were prepared on glass substrates for firing. The glasssubstrates were 2.5 mm thick soda lime glass as commercially availablefrom Libbey-Owens-Ford Co., Toledo, Ohio. A knife coater was used tocast a uniform slurry layer onto the glass substrates. The knife coatergap was set at 200 μm. The coatings were cured with a blue light for 1minute. The samples were then fired in a box furnace having an air flowof 30 scfh (standard cubic feet per hour). The firing schedule was 5° C.per minute to 540° C. for a 20 min soak. The samples were then cooled at2 to 3° C. per minute to room temperature. After firing, the fusedlayers were about 70 to 80 μm thick. The 10% sample, the formulation ofExample 3, was severely cracked to a point at which the fragments didnot adhere to the glass substrate after firing. The formulation ofExample 4, the 20% diluent sample, also cracked, but remained adhered tothe substrate. The formulations of Examples 5, 6, and 7 remained intactwithout cracking and were adhered to the substrate. These resultsindicate that higher diluent concentrations in a slurry allow morefacile binder burn out, presumably due to evaporation of the diluentleaving more pathways for debinding so that internal gas pressure fromvolatilization, which might otherwise cause fracturing, can be relieved.

Mold Release Properties

Mold release after curing was studied quantitatively with a peel testercommercially available from Instramentors, Inc., Strongville, Ohio,under the trade designation Model SP-102C-3M90. Sheets of a polymer moldhaving rectangular channels were used for forming rib structures fromthe glass slurries of Examples 3-7 onto soda lime glass substrates. Thechannels in the mold were nominally 75 μm wide, 185 μm deep, and 220 μmin pitch spacing. Sample fabrication involved laminating the glassslurry samples between the glass substrate and the mold, followed bycuring the samples. The slurry essentially filled the channels of themold during lamination to thereby replicate the mold features onto theglass substrate after curing. The molds were about 2.5 cm wide by about22 cm long. The channels were parallel to the long dimension of themolds. After lamination, the samples were cured using a blue lightsource for a dosage of 1-1.5 J/cm². After curing, the molds werereleased by peeling along the direction of the channels and the peelforce was measured. Peel test was performed at 90° to the substrate andat a speed of about 20 cm per minute. The average peel forcemeasurements are shown in Table 4.

TABLE 4 Example Diluent (% by weight) Peel Force (kg/cm) 3 10 moldfailure 4 20 0.71 5 30 0.47 6 35 0.16 7 40 0.10

The formulation of Example 3 did not give conclusive results because theadhesion to the mold was so strong that the mold tore in the peelprocess. The benefit of the diluent in enhancing mold release is evidentfrom Table 4. However, note that at very high diluent levels, thephysical integrity of the cured green state structures can be degradedsignificantly due to the relatively high liquid content. The formulationof Example 7 showed some defects after curing due to breakage of thegreen state structures. The formulations of Examples 4, 5, and 6,representing diluent contents above 10% and below 40%, exhibited thebest combination of green state physical integrity and mold releaseproperties.

Example 8

A spatula was used to mix an epoxy binder with 82.3% by weight (43.3volume %) of yttria-stabilized zirconia powder (commercially availablefrom Zirconia Sales America, grade HSY-3B). The average particle size inthe zirconia powder size was 0.4 microns. The epoxy binder was mixedwith a diluent and a surfactant in amounts of 54.2% by weight epoxy,36.4% by weight diluent and 9.4% by weight surfactant. The epoxy was ablend of bisphenol A epoxide (commercially available from CelaneseCorp., Louisville, Ky., under the trade designation Celanese DER 332)and an amine curing agent (commercially available from Celanese Corp.under the trade designation Epi-cure 826). The curing agent level was26% by weight of the epoxy. The diluent system was a blend of 65% byweight of 1,3 butanediol (commercially available from Aldrich ChemicalCo., Milwaukee, Wis.) and 35% by weight of polyethylene glycol(commercially available from Sigma Chemical, St. Louis, Mo., under thetrade designation Carbowax 200). The polyethylene glycol served tosolubilize the butanediol in the epoxy. The surfactant was a materialcommercially available from ICI Americas Inc., New Castle, Del., underthe trade designation hypermer KD1. The surfactant served to helpincorporate the zirconia powder in the resin. The slurry was molded ontoa plastic substrate, transferred onto an alumina substrate, and thendebinded by heating to 600° C. at a rate of 5° C. per minute. Thematerial was then fired by ramping the temperature to 1400° C. at a rateof 10° C. per minute and held there for 1 hour.

The slurry of Example 8 can be made by mixing the following materials inthe following amounts:

51.0 g yttria-stabilized zirconia powder

4.40 g bisphenol A epoxide

1.56 g curing agent

2.60 g polyethylene glycol

1.40 g 1,3 butanediol

1.02 g surfactant

Example 9

An acrylate binder was mixed with 85.5% by weight of yttria stabilizedzirconia powder. The zirconia powder was a bimodal blend of grade HSY-3B(as used in Example 8) with 12.3% by weight of grade HSY-3U ascommercially available from the same company. Grades HSY-3B and HSY-3Uhave respective average particle sizes of 0.4 and 0.1 microns. Thebinder was 50.5% of an acrylate resin (described below), 44.4% by weightdiluent and 5.0% by weight surfactant. Specifically, the resin was ablend of 50% by weight bisphenol A diglycidyl ether dimethacrylate(BISGMA) and 50% by weight triethylene glycol dimethacrylate (TEGMA).The cure initiator was a mixture of ethyl dimethylaminobenzoate,camphoroquinone and diphenyl iodonium hexafluorophosphate. The initiatorlevel was 2% by weight of the acrylate base resin. The diluent was 50%by weight diallyl phthalate and 50% by weight butyl strearate. Thediallyl phthalate plasticizer in the diluent served to reduce resinviscosity for improving moldability and to solubilize the butyl stearatein the acrylate resin. The butyl strearate in the diluent allowed forphase separation of the diluent upon curing of the binder to aid moldrelease and allow speedy egress of the binder material during debinding.The surfactant (available from ICI Americas under the trade designationhypermer KD1) was used to incorporate the zirconia powder into thebinder. The slurry was molded onto a glass substrate and cured byexposure to blue light through the substrate and through the mold for2.5 minutes before being demolded from the polymer mold that was used.The debinding and firing schedule was the same as used in Example 8.

The slurry of Example 9 can be made by mixing the following materials inthe following amounts:

510.10 g yttria stabilized zirconia powder grade HSY-3B

71.50 g yttria stabilized zirconia powder grade HSY-3U

50.00 g 50/50 BISGMA/TEGMA blend

22.20 g diallyl phthalate

22.20 g butyl stearate

5.00 g surfactant

Example 10

A uv curable oligomeric composition was used to form a microstructuredflexible mold. The composition was a mixture of 99% by weight of thealiphatic urethane acrylate, Photomer 6010, and 1% by weight of aphotoinitiator commercially available from Ciba Specialty Chemicalsunder the trade designation Darocur 1173. The oligomeric resin washeated to about 60° C. to lower the viscosity to about 2500 centipoise.The resin was poured along one edge of a metal tool having a positiveribbed microstructure suitable for use in PDP barrier rib formation andoverlaid with a polyester film having a 5 mil thickness. The stack waspulled between the flat surface on which the stack was placed and ametal roller mounted on a frame above the stack. The gap between theflat surface and the roller was adjusted such that the distance betweenthe metal tool and the polyester film was about 0.001 inches. As thestack was pulled through the gap, the oligomeric resin was forced intothe microstructure of the tool and spread across the tool. The stack wasirradiated through the polyester substrate using three passes under amedium-pressure mercury lamp for a dosage in the range of 200 to 400mJ/cm². The resulting microstructured mold was peeled away from themetal tool to provide a nearly exact negative of the microstructurepresent on the metal tool.

Example 11

A uv curable oligomeric composition was used to form a microstructuredflexible mold. The composition was a mixture of 75% by weight of thealiphatic urethane acrylate, Photomer 6010, 24% by weight of1,6-hexanediol diacrylate, and 1% by weight of the photoinitiatorDarocur 1173. The oligomeric resin was heated to about 60° C. to lowerthe viscosity to about 1000 centipoise. The resin was poured along oneedge of a metal tool having a positive ribbed microstructure andoverlaid with a polyester film having a 5 mil thickness. The stack waspulled between the flat surface on which the stack was placed and ametal roller mounted on a frame above the stack. The gap between theflat surface and the roller was adjusted such that the distance betweenthe metal tool and the polyester film was about 0.001 inches. As thestack was pulled through the gap, the oligomeric resin was forced intothe microstructure of the tooling and spread across the metal tool. Thestack was irradiated through the polyester substrate using three passesunder a medium-pressure mercury lamp for a dosage in the range of 200 to400 mJ/cm². The resulting microstructured mold was peeled away from themetal tool to reveal, upon further examination, distortedmicrostructures with concave shaped side-walls and slanted tops.

Example 12

The following is an example of compression molding to form patternedmicrostructured molds for use in the present invention. A sample wasprepared for compression molding by sequentially stacking the following:a cardboard sheet, a chrome-plated brass plate, a 9 inch by 13 inchmicrostructured metal tool, four sheets of 0.0055 inch thickpolycarbonate film (available from the Bayer Corp. under the tradedesignation Makrolon 2407), followed by a second chrome plated brassplate, and a second cardboard sheet.

The stack was placed in a compression molder (as commercially availablefrom Wabash MPI, Wabash, Id., under the trade designation ModelV75H-24-CLX), which was heated to 190° C. The stack was compressed at5000 lbs loading force for 2 minutes. The load was increased to 40,000lbs for an additional 2 minutes, followed by cooling to approximately80° C. under pressure. The stack was removed from the molder anddisassembled to provide a microstructured mold.

What is claimed is:
 1. A process for forming and aligningmicrostructures on a patterned substrate comprising the steps of:placing a mixture comprising a curable material between the patternedsubstrate and a patterned surface of a mold, the patterned surface ofthe mold having a plurality of microstructures thereon; stretching themold to align a portion of the patterned surface of the mold with aportion of the patterned substrate; curing the curable material to arigid state adhered to the substrate; and removing the mold to leavehardened structures of the mixture aligned with the pattern of thesubstrate, the hardened structures substantially replicating themicrostructures of the patterned surface of the mold.
 2. A process forforming and aligning ceramic microstructures on a patterned substratecomprising the steps of: providing a slurry comprising a mixture of aceramic powder and a curable fugitive binder; placing the slurry betweena patterned glass substrate and a patterned surface of a mold, thepatterned surface of the mold having a plurality of microstructuresthereon; stretching the mold to align a portion of the patterned surfaceof the mold with a portion of the patterned substrate; curing thecurable binder to harden the slurry and to adhere the slurry to thesubstrate; removing the mold to leave green state microstructures of theslurry adhered to the substrate, the green state microstructuressubstantially replicating the microstructures of the patterned surfaceof the mold.
 3. The process of claim 2, further comprising the steps ofdebinding the green state microstructures to substantially burn out thefugitive binder, and thereafter firing the green state microstructuresat an elevated temperature higher than that used for debinding to sinterthe ceramic powder to form ceramic microstructures.
 4. The process ofclaim 3, wherein the slurry further comprises a diluent selected topromote release properties with the mold during the removal step and tofacilitate burn out of the binder during the debinding step.
 5. Theprocess of claim 3, wherein the positions of the ceramic microstructureson the substrate after the firing step substantially match the positionsof the green state microstructures on the substrate before firing. 6.The process of claim 2, wherein the step of curing the curable bindercomprises exposing the slurry to ultraviolet or visible light radiationthrough the substrate, through the mold, or through both the substrateand the mold.
 7. The process of claim 2, wherein the step of stretchingthe mold comprises mechanically pulling the mold in a single directionlateral to the substrate.
 8. The process of claim 2, wherein the step ofstretching the mold comprises heating the mold in a substantiallyuniform fashion to thereby expand the mold.
 9. The process of claim 2,wherein the mold comprises a thermoplastic material having a smoothsurface and an opposing microstructured surface.
 10. The process ofclaim 2, wherein the mold comprises a base film layer and a patternedlayer made from a curable polymer, the patterned layer having a smoothsurface adhered to the base film layer and a microstructured surfaceopposing the base film layer.
 11. The process of claim 2, wherein theslurry further comprises a silane compound selected to promote adhesionwith the substrate during the curing step.
 12. The process of claim 2,wherein the patterned glass substrate comprises a series ofsubstantially parallel and independently addressable electrodes spaced adistance apart.
 13. The process of claim 12, wherein the microstructureof the patterned surface of the mold comprises a series of substantiallyparallel ridges protruding from the surface of the mold, the ridgeshaving dimensions and spacings such that the ridges are capable of beingaligned with the electrodes of the substrate during the step ofstretching the mold.
 14. The process of claim 13, wherein the step ofstretching the mold comprises mechanically expanding the mold in adirection parallel with the ridges of the mold.
 15. The process of claim13, wherein the step of stretching the mold comprises mechanicallyexpanding the mold in a direction perpendicular with the ridges of themold.
 16. The process of claim 13, wherein the step of removing the moldcomprises peeling the mold from the green state microstructures in adirection parallel with the ridges of the mold.